Pigment mixture, and use thereof in cosmetics, food and pharmaceuticals

ABSTRACT

The invention relates to pigment mixtures comprising at least two components A and B. The inventive pigment mixtures are characterized in that component A is embodied as effect pigments while component B is embodied as coloring agents and fillers. Also disclosed is the use of said pigment mixtures in cosmetic formulations and for coloring food products and pharmaceutical products.

The present invention relates to effect pigments based on flake-formsubstrates, and to the use thereof in mixtures with other colorantsand/or fillers in cosmetic formulations and in the foods andpharmaceuticals sector.

Gold pigments based on flake-form substrates are of importance, inparticular, in printing applications and in cosmetics. Frequently,however, the gold pigments known from the prior art exhibit thedisadvantage that they do not have a sufficiently intense colour andbrightness and therefore do not cause a truly golden optical impressionin the various application media.

The object of the present invention is to find gold pigments forcosmetics which are distinguished by a more intense golden lustre and donot have the above-mentioned disadvantages. A further object of theinvention is to find formulations in which the golden lustre issupported in a particularly advantageous manner or modified in anoptically attractive manner.

Surprisingly, it has now been found that pigment mixtures comprisingeffect pigments, preferably gold pigments, based on multicoatedflake-form substrates in combination with further colorants and/orfillers impart a very soft skin feel, are light-stable, do notbleed/migrate, are non-toxic and have high hiding power. The pigmentsare distinguished by the fact that they have alternating high- andlow-refractive-index layers and comprise at least onehigh-refractive-index coating consisting of a mixture of TiO₂ and Fe₂O₃in the molar ratio 1:0.5 to 1:2.0.

Gold pigments based on multicoated flake-form substrates are disclosed,for example, in WO 01/30921.

The use of the multilayer pigment having a golden mass tone incombination with organic and inorganic fillers and/or with flake-form,needle-shaped, spherical or crystalline colorants enables colour effectsto be enhanced and novel colour effects to be achieved. Furthermore, thepigment mixtures are distinguished by their high lustre and a very goodskin feel.

The invention thus relates to a pigment mixture consisting of at leasttwo components A and B, where

-   -   component A comprises effect pigments based on multicoated        flake-form substrates which have a layer sequence comprising        -   (A) a high-refractive-index coating consisting of a mixture            of TiO₂ and Fe₂O₃ in the molar ratio 1:0.5 to 1:2.0 and            optionally one or more metal oxide(s) in amounts of <20% by            weight, based on layer (A),        -   (B) a colourless coating having a refractive index n<1.8,        -   (C) a colourless coating having a refractive index n>1.8,        -   (D) an absorbent coating having a refractive index n>1.8        -   and optionally        -   (E) an outer protective layer,        -   and    -   component B comprises colorants selected from the group of        inorganic pigments, organic pigments, dyes, colouring natural        fruit and/or plant extracts and/or fillers which consist of        flake-form, needle-shaped, spherical or irregularly shaped        particles.

The outstanding colouristic parameter of the pigment mixture is thestrong, preferably purely golden, colour together with an optimum lustreeffect and/or silk effect. The pigments of component A preferably haveLab values in the range from L=60 to 85; a=−15 to 25; b=22 to 45(measurement method: Phyma, 22.5°/22.5° on a black background).

The invention likewise relates to cosmetic formulations, such as, forexample, make-up, compact powders, loose powders, lipsticks, lotions,emulsions, etc., which comprise the pigment mixture according to theinvention. The pigment mixtures are furthermore suitable for colouringfoods and pharmaceutical products, including OTC preparations, and forcolouring coatings of food and pharmaceutical products, including OTCpreparations, such as, for example, medicament coatings of tablets,dragees, gelatine capsules, etc.

The effect pigments of component A can be mixed with the colorant orfiller in any ratio. The mixing ratio of component A to component B ispreferably 99:1 to 50:50, in particular 95:5 to 70:30, very particularlypreferably 70:30 to 50:50. If component B comprises fillers, the ratioof component A:B may also be 99:1 to 1:99.

Preferred effect pigments of component A have the following structure;

substrate+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃/TiO₂

substrate+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃

substrate+Fe₂O₃/TiO₂+SiO₂+TiO₂+SiO₂+Fe₂O₃/TiO₂

Layers (A) to (D) or (A) to (E) are preferably applied directly to thesubstrate surface, i.e. layer (A) is located directly on the substratesurface.

In order to improve the pigment properties, such as lustre andbrightness, interlayers (ILs) can optionally be applied, for example alayer of TiO₂, preferably with layer thicknesses of 1-100 nm, inparticular 1-80 nm and very particularly preferably 1-50 nm, or a layerof SiO₂, preferably with layer thicknesses of 5-100 nm, can be appliedto the substrate. In this case, particular preference is given to alayer structure comprising

substrate+(IL)TiO₂+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃/TiO₂

substrate+(IL)TiO₂+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃

The present invention likewise relates to these effect pigments havingan interlayer and to the use thereof in paints, coatings, printing inks,plastics, in cosmetic formulations and for colouring food andpharmaceutical products.

Suitable base substrates for the effect pigments of component A are onthe one hand opaque and on the other hand transparent flake-formsubstrates. Preferred substrates are phyllosilicates and glass flakes.Particularly suitable are natural and/or synthetic mica, talc, kaolin,flake-form iron or aluminium oxides, glass flakes, SiO₂ flakes, SiO_(x)flakes (0.70≦x≦2.0), preferably SiO₂ flakes, TiO₂ flakes, graphiteflakes, synthetic support-free flakes, liquid crystal polymers (LCPs),holographic pigments, BiOCl flakes, metal flakes, optionally passivated,such as, for example, aluminium flakes, flakes of aluminium bronzes,brass bronzes, zinc bronzes, titanium bronzes or other comparablematerials.

The size of the base substrates is not crucial per se and can be matchedto the particular application. In general, the flake-form substrateshave a thickness between 0.02 and 5 μm, in particular between 0.05 and4.5 μm. The size in the other two dimensions is usually between 1 and250 μm, preferably between 2 and 200 μm, and in particular between 5 and150 μm. Glass flakes preferably have a layer thickness of ≦1.0 μm, inparticular ≦0.8 μm and very particularly preferably ≦0.5 μm.

The effect pigments have a high-refractive-index coating (A) consistingof a mixture of TiO₂ and Fe₂O₃, preferably in the molar ratio 1:1, incombination with a colourless low-refractive-index coating (B)alternating on the substrate. Layer (A) can be converted intopseudobrookite or a mixture of pseudobrookite with TiO₂ orpseudobrookite with Fe₂O₃ by suitable measures known to the personskilled in the art, such as, for example, calcination of the pigments attemperatures >800° C.

Layer (C) preferably consists of TiO₂, ZrO₂, SnO₂, Ce₂O₃, BiOCl ormixtures or combinations thereof. In the case where layer (C) consistsof TiO₂, the TiO₂ is preferably in the rutile modification.

Suitable materials for layer (D) are absorbent materials, such asmetals, for example iron, tungsten, chromium, cobalt, nickel, copper,silver, gold, aluminium and alloys thereof, metal oxides, such as, forexample, CoO, Co₃O₄, Fe₂O₃, Fe₃O₄, pseudobrookite, TiO₂/Fe₂O₃ mixture,VO₂, V₂O₃, metal sulfides, such as, for example, molybdenum sulfide,iron sulfide, tungsten sulfide, chromium sulfide, cobalt sulfide, nickelsulfide and mixtures of these sulfides. The absorbent layer (D) ispreferably a mixture of TiO₂ and Fe₂O₃, where the mixing ratios, like inthe case of layer (A), can be varied in broad limits. The TiO₂ to Fe₂O₃molar ratio is preferably 1:1. Layer (D) can be converted intopseudobrookite or a mixture of pseudobrookite with TiO₂ orpseudobrookite with Fe₂O₃ by suitable measures analogously to layer (A),such as, for example, calcination of the pigments at temperatures >800°C. This layer (D) has a refractive index of n>1.8, in particular n≧2.0.

A further colourless low-refractive-index layer (B*), which may beidentical to or different from layer (B), may be located between layers(C) and (D).

The high-refractive-index layer (A) preferably has a refractive index ofn>1.8, in particular n≧2.0, and is a mixture of TiO₂ and Fe₂O₃, wherethe mixing ratio is 1:0.5 to 1:2.0, preferably 1:0.7 to 1:1.5, inparticular 1:1. Layer (A) is preferably intensely colouredpseudobrookite. The thickness of layer (A) is preferably 10 to 300 nm,preferably 15 to 250 nm and in particular 20 to 200 nm.

In order to increase the tinting strength of layer (A), it is alsoadvisable to admix one or more metal oxides from the group Al₂O₃, Ce₂O₃,B₂O₃, ZrO₂, SnO₂. The % by weight proportion of the further metaloxides, besides the Fe₂O₃/TiO₂ mixture, should be not greater than 20%by weight, preferably not greater than 10% by weight.

In the case where layer (D) is likewise a layer of a TiO₂/Fe₂O₃ mixture,it is likewise advisable to add one or more metal oxides, such as, forexample, Al₂O₃, Ce₂O₃, B₂O₃, ZrO₂, SnO₂, in amounts of not greater than20% by weight, based on layer (D), in order to increase the tintingstrength.

Suitable colourless low-refractive-index materials which are suitablefor coating (B) are preferably metal oxides or the corresponding oxidehydrates, such as, for example, SiO₂, Al₂O₃, AlO(OH), B₂O₃, MgF₂, MgSiO₃or a mixture of the said metal oxides. The thickness of layer (B) is 10to 600 nm, preferably 20 to 500 nm and in particular 20 to 400 nm.

If layer (C) is a TiO₂ layer, this is preferably in the rutilemodification. The processes for the preparation of rutile are describedin the prior art, for example in U.S. Pat. No. 5,433,779, U.S. Pat. No.4,038,099, U.S. Pat. No. 6,626,989, DE 25 22 572 C2, EP 0 271 767 B1.Before the precipitation of TiO₂ onto layer (B), a thin layer of tinoxide is preferably applied (layer B*), which serves as additive forconversion of the TiO₂ into rutile.

The effect pigments can be prepared, for example, as described in WO01/30921.

The coating of the substrate flakes with layers (A)-(D) can be carriedout by wet-chemical methods and/or by CVD methods. Before theapplication of layer (A), a thin dielectric layer where n<1.8 canoptionally also be deposited. A coating of this type, for example onglass flakes, can consist, for example, of an SiO₂ layer with athickness of 5-100 nm.

The effect pigments are preferably prepared using the wet-chemicalmethod, it being possible to use the known wet-chemical coatingtechnologies which were developed for the preparation of pearlescentpigments and are described, for example, in the following publications:DE 14 67 468, DE 19 59 988, DE 20 09 566, DE 22 14 545, DE 22 15 191, DE22 44 298, DE 23 13 331, DE 25 22 572, DE 31 37 808, DE 31 37 809, DE 3151 343, DE 31 51 354, DE 31 51 355, DE 32 11 602, DE 32 35 017.

In the case of wet coating, the substrate particles are suspended inwater, and one or more hydrolysable metal salts are added at a suitablepH for the hydrolysis, which is selected so that the metal oxides ormetal oxide hydrates are precipitated directly onto the flakes withoutsignificant secondary precipitations occurring. During the coatingoperation, the substrate particles are kept in motion in order that ahomogeneous coating of the substrate particles is ensured and thesubstrate is completely enveloped and no open edges remain. The pH isusually kept constant by simultaneous metered addition of a base and/oracid. The pigments are subsequently separated off, washed and preferablydried at 50-180° C. and optionally calcined, where the calcinationtemperature must be optimised with respect to the coating present ineach case and the substrate used. In general, the calcinationtemperatures are between 250 and 1000° C., preferably between 350 and900° C. If desired, the pigments can be separated off after applicationof individual coatings, dried and optionally calcined and thenre-suspended for the precipitation of further layers.

Furthermore, the coating can also be carried out in a fluidised-bedreactor by gas-phase coating, where the processes proposed, for example,in EP 0 045 851 A1 and EP 0 106 235 A1 for the preparation ofpearlescent pigments can be used correspondingly. It is necessary herefor the substrate to be kept uniformly in motion during the coatingoperation in order that homogeneous coating of all particle surfaces isensured and the substrate is completely enveloped and no open edgesremain.

The effect pigments of component A can also be provided with an organicor inorganic protective layer (layer E) in order to improve the light,weather and chemical stability or in order to increase the compatibilityin various media. Suitable post-coatings or post-treatments are, forexample, silanes, silicones, adsorbent silicones, metal soaps, aminoacids, lecithins, fluorine components, polyethylenes, collagen or themethods described in DE 22 15 191, DE 31 51 354, DE 32 35 017 or DE 3334 598, EP 0 632 109, U.S. Pat. No. 5,759,255, DE 43 17 019, DE 39 29423, EP 0 492 223, EP 0 342 533, EP 0 268 918, EP 0 141 174, EP 0 764191, WO 98/13426 or EP 0 465 805. This post-coating further increasesthe chemical and photochemical stability or simplifies handling of thegold pigment, in particular incorporation into various media. In orderto improve the wettability, dispersibility and/or compatibility with theuser media, it is possible to apply, for example, functional coatings ofAl₂O₃ or ZrO₂ or mixtures or mixed phases thereof to the pigmentsurface. Organic or combined organic/inorganic post-coatings, forexample with silanes, as described, for example, in EP 0090259, EP 0 634459, WO 99/57204, WO 96/32446, WO 99/57204, U.S. Pat. No. 5,759,255,U.S. Pat. No. 5,571,851, WO 01/92425 or in J. J. Ponjeé, PhilipsTechnical Review, Vol. 44, No. 3, 81 ff. and P. H. Harding J. C. Berg,J. Adhesion Sci. Technol, Vol. 11 No. 4, pp. 471-493, are furthermorepossible. The additionally applied substances make up only about 0.1 to5% by weight, preferably 0.5 to 3.0% by weight, of the entire pigment.

The post-coating of the effect pigments can be carried out directly in aone-pot process onto layer (D). However, it is also possible firstly toisolate, optionally dry and calcine the multilayer pigment andsubsequently to apply the post-coating.

Besides the effect pigment, preferably a gold pigment (component A),pigment mixtures according to the invention comprise a filler and/or acolorant of component B.

Suitable as component B for the pigment mixture according to theinvention are all flake-form, needle-shaped, spherical and crystallinecolorants or fillers which are known to the person skilled in the art,in particular those which have a particle size of 0.001 to 10 μm,preferably 0.01 to 1 μm. Colorants are taken to mean inorganic andorganic colorants in accordance with DIN standard 55944. In thisapplication, colorants are also taken to mean colouring natural fruitand plant extracts.

The pigment mixtures according to the invention preferably comprise, ascolorants, inorganic dyes and inorganic pigments, such as, for example,inorganic white pigments, inorganic coloured pigments, inorganic blackpigments, inorganic effect pigments. The latter are of course notidentical with the pigments of component A. Besides the inorganiccolorants, organic colorants, such as, for example, organic pigments,such as, for example, coloured pigments, black pigments, effectpigments, and inorganic dyes, such as, for example, coloured dyes, blackdyes, are also suitable. Suitable fillers are preferably flake-form orspherical materials.

Component B preferably comprises coated or uncoated SiO₂ beads. SiO₂beads coated with one or more metal oxides are disclosed, for example,in EP 0 803 550 A2.

The colorants of component B are furthermore preferably inorganic effectpigments, such as, for example, pearlescent pigments, includingmultilayer pigments or interference pigments, which are not identicalwith component (A). The pearlescent pigments used are pigments based onflake-form, transparent or semitransparent substrates comprising, forexample, phyllosilicates, such as, for example, natural or syntheticmica, talc, sericite, kaolin or other silicate materials, coated withcoloured or colourless metal oxides, such as, for example, TiO₂,titanium suboxides, titanium oxynitrides, Fe₂O₃, Fe₃O₄, FeOOH, SnO₂,Cr₂O₃, ZnO, CuO, NiO, and other metal oxides, alone or in a mixture, ina single layer or in successive layers.

Pearlescent pigments are disclosed, for example, in German patents andpatent applications 14 67 468, 19 59 998, 20 09 566, 22 14 454, 22 15191, 22 44 298, 23 13 331, 25 22 572, 31 37 808, 31 37 809, 31 51 343,31 51 354, 31 51 355, 32 11 602, 32 35 017 and P 38 42 330 and arecommercially available, for example under the trademarks Iriodin®,Timiron®, Xirona® from Merck KGaA, Darmstadt, Germany and/or Rona, USA.Part icularly preferred pigment compositions comprise TiO₂/mica,Fe₂O₃/mica and/or TiO₂/Fe₂O₃/mica pigments. The pearlescent pigments mayadditionally have a layer of Berlin Blue or Carmine Red on the surface.

Preference is furthermore given to coated or uncoated BiOCl pigments,TiO₂- and/or Fe₂O₃-coated SiO₂, glass or Al₂O₃ flakes. The coating ofthe SiO₂ flakes with one or more metal oxides can be carried out, forexample, as described in WO 93/08237 (wet-chemical coating) or DE-A 19614 637 (CVD method).

The multilayer pigments disclosed, for example, in DE-A 196 18 563, DE-A196 18 566, DE-A 196 18 569, DE-A 197 07 805, DE-A 197 07 806, DE-A 19746 067 are based on a flake-form, transparent, coloured or colourlessmatrix consisting of mica (synthetic or natural), SiO₂ flakes, glassflakes, Al₂O₃ flakes, polymer flakes and generally have a thicknessbetween 0.3 and 5 μm, in particular between 0.4 and 2.0 μm. The size inthe other two dimensions is usually between 1 and 250 μm, preferablybetween 2 and 100 μm, and in particular between 5 and 40 μm. Themultilayer pigments consist of the matrix (substrate) coated with metaloxides (at least 2). The coating of the substrate flakes mica, SiO₂flakes, glass flakes, Al₂O₃ flakes with a plurality of layers is carriedout in such a way that a layer structure preferably consisting ofalternating high- and low-refractive-index layers is formed. Themultilayer pigments preferably contain 2, 3, 4, 5, 6 or 7 layers, inparticular 3, 4 or 5 layers. Suitable high-refractive-index metal oxidesare, for example, titanium dioxide, zirconium oxide, zinc oxide, ironoxides, iron/titanium oxides (iron titanates) and/or chromium oxide, inparticular TiO₂ and/or Fe₂O₃. The low-refractive-index oxides used areSiO₂ and Al₂O₃. However, it is also possible to employ MgF₂ or anorganic polymer (for example acrylate) for this purpose. The coating ofthe substrate flakes can be carried out, for example, as described in WO93/08237 (wet-chemical coating) or DE-A-196 14 637 (CVD method).Particularly preferred multilayer pigments based on mica (natural orsynthetic), glass flakes, Al₂O₃ flakes, Fe₂O₃ flakes, SiO₂ flakescomprise a layer sequence TiO₂—SiO₂—TiO₂, The TiO₂ can be in either theanatase or the rutile modification. It is preferably in the form ofrutile.

The interference pigments are preferably pigments based on mica, glassflakes, SiO₂ flakes which are coated with coloured or colourless metaloxides, such as, for example, TiO₂, titanium suboxides, titaniumoxynitrides, Fe₂O₃, Fe₃O₄, SnO₂, Cr₂O₃, ZnO, CuO, NiO, and other metaloxides, alone or in a mixture, in a single layer or in successivelayers.

Suitable flake-form colorants are, in particular, pearlescent pigments,in particular based on mica, SiO₂ flakes or Al₂O₃ flakes, which are onlycovered with one metal-oxide layer, metal-effect pigments (Al flakes,bronzes), optically variable pigments (OVPs), liquid-crystal polymerpigments (LCPs) or holographic pigments.

The spherical colorants include, in particular, TiO₂, coloured SiO₂,CaSO₄, iron oxides, chromium oxides, carbon black, organic colouredpigments, such as, for example, anthraquinone pigments, quinacridonepigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, azopigments, isoindoline pigments. The needle-shaped pigments arepreferably BiOCl, coloured glass fibres, α-FeOOH, organic colouredpigments, such as, for example, azo pigments, β-phthalocyanine CI Blue15.3, Cromophtal Yellow 8GN (Ciba), Irgalith Blue PD56 (Ciba),azomethine copper complex CI Yellow 129, Irgazine Yellow 5GT (Ciba).

It is likewise possible to admix nanoscale dielectrics in order toimprove the skin feel. Examples of admixtures of this type are Al₂O₃,SiO₂, ZnO or TiO₂, which are usually added to the formulation in amountsof 0.01-15%.

The pigment mixture according to the invention is simple and easy tohandle. The pigment mixture can be incorporated into the applicationsystem by simple stirring-in. Components A and B can be added to theapplication system simultaneously, successively or as a mixture. Complexgrinding and dispersion of the pigments is unnecessary.

The pigment mixture according to the invention can preferably be usedfor pigmenting food colourings, for the finishing of foods, for examplemass colouring or as a coating, in medicament coatings, for example indragees and tablets, or in cosmetic formulations, such as lipsticks, lipgloss, eyeliner, eye shadow, rouge, sunscreen, pre-sun and after-suncompositions, make-ups, body lotions, bath gels, soaps, bath salts,toothpaste, hair gels, (volume) mascara, nail varnishes, compactpowders, shampoos, loose powders and gels, etc.

The concentration of the pigment mixture in the application system to bepigmented is generally between 0.01 and 70% by weight, preferablybetween 0.1 and 50% by weight and in particular between 1.0 and 10% byweight, based on the total solids content of the system. It is generallydependent on the specific application and can be up to 100% in the caseof loose powders. The use concentration of the pigment mixture accordingto the invention extends from 0.01% by weight in shampoos to 70% byweight in compact powders. In a mixture of the multilayer pigments ofcomponent A with spherical fillers, for example SiO₂, the concentrationcan be 0.01-70% by weight in the formulation. The cosmetic products,such as, for example, nail varnishes, lipsticks, compact powders,shampoos, loose powders and gels, are distinguished by particularlyinteresting lustre effects.

The pigment mixture according to the invention can advantageously beemployed in both decorative and care cosmetics. The use concentrationand the mixing ratio of the multilayer pigments of component A withcomponent B, in particular organic and inorganic coloured pigments anddyes, of natural or synthetic origin, such as, for example, chromiumoxide, ultramarine, spherical SiO₂ or TiO₂ pigments, are dependent onthe application medium and the effect to be achieved.

The effect pigment of component A can furthermore be mixed withcommercially available fillers. Fillers which may be mentioned are, forexample, natural and synthetic mica, glass beads or glass powder, nylonpowder, pure or filled melamine resins, talc, glasses, kaolin, oxides orhydroxides of aluminium, magnesium, calcium or zinc, BiOCl, bariumsulfate, calcium sulfate, calcium carbonate, magnesium carbonate,carbon, and physical or chemical combinations of these substances.

There are no restrictions regarding the particle shape of the filler. Inaccordance with requirements, it can be, for example, flake-form,spherical, needle-shaped, crystalline or amorphous.

The pigment mixture according to the invention can of course also becombined in the formulations with cosmetic raw materials and assistantsof any type. These include, inter alia, oils, fats, waxes, film formers,surfactants, antioxidants, such as, for example, vitamin C or vitamin E,stabilisers, odour enhancers, silicone oils, emulsifiers, solvents, suchas, for example, ethanol or ethyl acetate or butyl acetate,preservatives and assistants which generally determine applicationalproperties, such as, for example, thickeners and rheological additives,such as, for example, bentonites, hectorites, silicon dioxides, Casilicates, gelatines, high-molecular-weight carbohydrates and/orsurface-active assistants, etc.

The formulations comprising the pigment mixtures according to theinvention can belong to the lipophilic, hydrophilic or hydrophobic type.In the case of heterogeneous formulations having discrete aqueous andnon-aqueous phases, the pigment mixtures according to the invention mayin each case be present in only one of the two phases or alternativelydistributed over both phases.

The pH of the formulations can be between 1 and 14, preferably between 2and 11 and particularly preferably between 5 and 8.

No limits are set for the concentrations of the pigment mixturesaccording to the invention in the formulation. They can be—depending onthe application—between 0.001 (rinse-off products, for example showergels) and 100% (for example lustre-effect articles for particularapplications).

The pigment mixture according to the invention can furthermore also becombined with cosmetic active compounds. Suitable active compounds are,for example, insect repellents, inorganic UV filters, such as, forexample, TiO₂, UV NBC protective filters (for example OMC, B3, MBC),also in encapsulated form, anti-ageing active compounds, vitamins andderivatives thereof (for example vitamin A, C, E, etc.), self-tanningagents (for example DHA, erythrulose, inter alia), and further cosmeticactive compounds, such as, for example, bisabolol, LPO, VTA, ectoine,emblica, allantoin, bioflavonoids and derivatives thereof. Organic UVfilters are generally incorporated into cosmetic formulations in anamount of 0.5 to 10% by weight, preferably 1-8% by weight, and inorganicfilters in an amount of 0.1 to 30% by weight, based on the formulationas a whole.

The compositions according to the invention may in addition comprisefurther conventional skin-protecting or skin-care active compounds.These may in principle be any active compounds known to the personskilled in the art.

Particularly preferred active compounds are pyrimidinecarboxylic acidsand/or aryl oximes.

Of the cosmetic applications, particular mention should be made of theuse of ectoine and ectoine derivatives for the care of aged, dry orirritated skin. Thus, EP-A-0 671 161 describes, in particular, thatectoine and hydroxy-ectoine are employed in cosmetic compositions, suchas powders, soaps, surfactant-containing cleansing products, lipsticks,rouge, make-up, care creams and sunscreen preparations. The cosmeticformulations according to the invention preferably comprise 0.05-5% byweight, in particular 0.1-3% by weight, of ectoine or ectoinederivatives, based on the formulation.

Application forms of the cosmetic formulations which may be mentionedare, for example: solutions, suspensions, emulsions, PIT emulsions,pastes, ointments, gels, creams, lotions, powders, soaps,surfactant-containing cleansing preparations, oils, aerosols and sprays.Examples of other application forms are sticks, shampoos and showerpreparations. Any desired customary vehicles, assistants and, ifdesired, further active compounds may be added to the composition.

Ointments, pastes, creams and gels may comprise the customary vehicles,for example animal and vegetable fats, waxes, paraffins, starch,tragacanth, cellulose derivatives, polyethylene glycols, silicones,bentonites, silica, talc and zinc oxide, or mixtures of thesesubstances.

Powders and sprays may comprise the customary vehicles, for examplelactose, talc, silica, aluminium hydroxide, calcium silicate andpolyamide powder, or mixtures of these substances. Sprays mayadditionally comprise the customary propellants, for examplechlorofluorocarbons, propane/butane or dimethyl ether.

Solutions and emulsions may comprise the customary vehicles, such assolvents, solubilisers and emulsifiers, for example water, ethanol,isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzylbenzoate, propylene glycol, 1,3-butyl glycol, oils, in particularcottonseed oil, peanut oil, wheatgerm oil, olive oil, castor oil andsesame oil, glycerol fatty acid esters, polyethylene glycols and fattyacid esters of sorbitan, or mixtures of these substances.

Suspensions may comprise the customary vehicles, such as liquiddiluents, for example water, ethanol or propylene glycol, suspensionmedia, for example ethoxylated isostearyl alcohols, polyoxyethylenesorbitol esters and polyoxyethylene sorbitan esters, microcrystallinecellulose, aluminium metahydroxide, bentonite, agar-agar and tragacanth,or mixtures of these substances.

Soaps may comprise the customary vehicles, such as alkali metal salts offatty acids, salts of fatty acid monoesters, fatty acid proteinhydrolysates, isothionates, lanolin, fatty alcohol, vegetable oils,plant extracts, glycerol, sugars, or mixtures of these substances.

Surfactant-containing cleansing products may comprise the customaryvehicles, such as salts of fatty alcohol sulfates, fatty alcohol ethersulfates, sulfosuccinic acid monoesters, fatty acid proteinhydrolysates, isothionates, imidazolinium derivatives, methyl taurates,sarcosinates, fatty acid amide ether sulfates, alkylamidobetaines, fattyalcohols, fatty acid glycerides, fatty acid diethanolamides, vegetableand synthetic oils, lanolin derivatives, ethoxylated glycerol fatty acidesters, or mixtures of these substances.

Face and body oils may comprise the customary vehicles, such assynthetic oils, such as, for example, fatty acid esters, fatty alcohols,silicone oils, natural oils, such as vegetable oils and oily plantextracts, paraffin oils, lanolin oils, or mixtures of these substances.

The cosmetic compositions may exist in various forms. Thus, they can be,for example, a solution, a water-free composition, an emulsion ormicroemulsion of the water-in-oil (W/O) type or of the oil-in-water(O/W) type, a multiple emulsion, for example of thewater-in-oil-in-water (W/O/W) type, a gel, a solid stick, an ointment oran aerosol. It is also advantageous to administer ectoines inencapsulated form, for example in collagen matrices and otherconventional encapsulation materials, for example as celluloseencapsulations, in gelatine, wax matrices or liposomally encapsulated.In particular, wax matrices, as described in DE-A 43 08 282, have provenfavourable. Preference is given to emulsions. O/W emulsions areparticularly preferred. Emulsions, W/O emulsions and O/W emulsions areobtainable in a conventional manner.

Further embodiments are oily lotions based on natural or synthetic oilsand waxes, lanolin, fatty acid esters, in particular triglycerides offatty acids, or oily/alcoholic lotions based on a lower alcohol, such asethanol, or a glycerol, such as propylene glycol, and/or a polyol, suchas glycerol, and oils, waxes and fatty acid esters, such astriglycerides of fatty acids.

Solid sticks consist of natural or synthetic waxes and oils, fattyalcohols, fatty acids, fatty acid esters, lanolin and other fattysubstances.

If a composition is formulated as an aerosol, the customary propellants,such as alkanes, fluoroalkanes and chlorofiuoroalkanes, are generallyused.

The cosmetic composition may also be used to protect the hair againstphotochemical damage in order to prevent colour changes, bleaching ordamage of a mechanical nature. In this case, a suitable formulation isin the form of a rinse-out shampoo, lotion, gel or emulsion, thecomposition in question being applied before or after shampooing, beforeor after colouring or bleaching or before or after permanent waving. Itis also possible to select a composition in the form of a lotion or gelfor styling and treating the hair, in the form of a lotion or gel forbrushing or blow-waving, in the form of a hair lacquer, permanent wavingcomposition, colorant or bleach for the hair. The composition havinglight-protection properties may comprise adjuvants, such as surfactants,thickeners, polymers, softeners, preservatives, foam stabilisers,electrolytes, organic solvents, silicone derivatives, oils, waxes,antigrease agents, dyes and/or pigments which colour the compositionitself or the hair, or other ingredients usually used for hair care.

The pharmaceutical and food products are coloured by adding the pigmentmixture according to the invention, preferably comprising at least onegold pigment (component (A)) and a colorant from the area of the naturalor nature-identical dyes (component (B)), in the desired mixing ratios,to the product to be coloured in amounts of 0.005 to 15% by weight,preferably 0.01 to 100% by weight.

The admixing of natural or nature-identical dyes, organic or inorganiccoloured pigments (component (B)) or colouring natural fruit and plantextracts approved for the foods sector enables the colour effect of thegold pigment in the product to be influenced and at the same timeenables novel iridescent colour effects to be achieved.

Suitable natural or nature-identical dyes for the pigment mixtureaccording to the invention are, in particular, E 101, E 104, E 110, E124, E 131, E 132, E 140, E 141, E 151, E 160a. Suitable colouredpigments for the pigment mixture according to the invention are, forexample, E 171, E 172, E 153.

The proportion of dyes besides the gold pigment, based on the food orpharmaceutical product, is preferably in the range from 0.5 to 25% byweight. The dye employed can likewise be fruit and plant extracts, suchas, for example, carrot juice, beetroot juice, elderberry juice,hibiscus juice, paprika extract, aronia extract.

The total concentration of all pigments in the product to be pigmentedshould not exceed 50% by weight, based on the product. It is generallydependent on the specific application.

Various active-compound additives, such as, for example, vitamins,enzymes, trace elements, proteins, carbohydrates, essential fats and/orminerals, can also be added to the food and pharmaceutical products,where the total amount of active compounds, based on the food orpharmaceutical product, should not exceed 25% by weight. The amount ofactive compounds or active-compound mixtures is preferably 0.01-20% byweight, based on the product.

The products are coloured by adding the pigment mixture according to theinvention, alone or in combination with assistants, cosmetic activecompounds, ingredients, etc., to the product to be coloured, directly orin the presence of water and/or an organic solvent, in the desiredmixing ratios, simultaneously or successively, during or afterproduction thereof, before or after shaping (for example duringextrusion, pelleting, expansion, granulation, etc.). Admixing of theeffect pigments with pulverulent or loose powders is likewise possible.

The pigment mixture according to the invention can also be applied tothe surface for colouring food and pharmaceutical products aftershaping. In this case, the pigment mixture according to the invention isgenerally mixed with an application medium and subsequently applied tothe product using suitable application and spray devices. Theapplication or coating medium then ensures corresponding adhesion of thepigment mixture to the product surface. The latter is then colouredcorrespondingly.

On incorporation into the product matrix itself, the amount of thepigment mixture according to the invention used is preferably 0.5-40% byweight, in particular 1-30% by weight. In the case of surface colouringof food and pharmaceutical products, the use range in the colouring orcoating solution used is 0.1-25% by weight, in particular 1-15% byweight. On use of the pigment mixture according to the invention inpulverulent products, the use range is 0.05-50% by weight, in particular2-10% by weight.

The coating solutions preferably comprise water or organic solvents,such as, for example, ethanol or isopropanol. The film former employedin the coating solutions is preferably a cellulose derivative, such as,for example, hydroxypropylmethylcellulose. Particular preference isgiven to application solutions comprising cellulose derivatives which,instead of water, comprise 5-80% by weight of a suitable organicsolvent.

Compared with aqueous coating solutions, the alcoholic oralcoholic-aqueous, cellulose-containing application solutions havesignificant applicational advantages:

-   -   use of cooler drying air during the spray application    -   colouring of heat-sensitive products, such as, for example,        vitamin-containing foods, with the gold pigments is very readily        possible.

Products which are suitable for colouring that may be mentioned are, inparticular, coatings on all types of foods, in particular pigmentedsugar and shellac coatings (alcoholic and aqueous), coatings with oilsand waxes, with gum arabic and with cellulose grades (for exampleHPMC=hydroxypropylmethylcellulose), with starch and albumin derivatives,carrageenan and other substances known to the person skilled in the artwhich are suitable for coating. The pigment mixture according to theinvention is generally mixed with the application medium here andsubsequently applied to the food or pharmaceutical product usingsuitable application and spray devices, or by hand. The application orcoating medium then ensures corresponding adhesion of the pigments tothe food or pharmaceutical product surface.

The latter is then coloured correspondingly. The application and coatingsolutions preferably comprise 0.1-20% by weight, in particular 2-15% byweight, of pigment mixture.

Preferred dry powder mixtures for coatings comprise a cellulosederivative, such as, for example, hydroxypropylmethylcellulose, sodiumcarboxymethylcellulose, a release agent, such as, for example, lecithinor stearic acid, a lustre enhancer, such as, for example, maltodextrinand/or dextrose, and the pigment mixture according to the invention. Drypowder mixtures of this type preferably comprise the pigment mixture inamounts of 0.01-50% by weight, in particular 0.5-40% by weight, based onthe powder mixture. If necessary, dyes, flavourings, vitamins,sweeteners, etc., can also be added to these dry powder mixtures.

Products which are suitable for colouring or coating are, for example,sugar products, cake decorations, compresses, dragees, chewing gum, gumproducts, fondant products, marzipan products, filling compositions,cocoa and fat glazes, chocolate and chocolate-containing products, icecream, cereals, snack products, coating compositions, cake glazes,scattered sugar decorations, nonpareils, jelly and gelatine products,sweets, liquorice, icing, candyfloss, fat, sugar and cream compositions,blancmange, desserts, flan glaze, cold fruit soups, soft drinks andcarbonated beverages, beverages with stabilising additives, such as, forexample, carboxymethylcellulose, acidified and unacidified milkproducts, such as, for example, quark, yoghurt, cheese, cheese rinds,sausage casings, etc.

In the case of coated food and pharmaceutical products, it is possibleto combine the pigment mixture according to the invention with aromasubstances (powder or liquid aromas), acids and/or with sweeteners, suchas, for example, aspartame, in order additionally to reinforce thevisual effect in terms of flavour.

The invention thus relates to all formulations from the foods andpharmaceuticals sector comprising the effect pigment of component A withfurther pigments, fillers or dyes (natural or nature-identical),colouring natural fruit and plant extracts, as colorants of component B.

A further major area of application is in the pharmaceuticals and OTCsector for colouring or as a coating for tablets, gelatine capsules,dragees, ointments, cough mixture, etc. In combination with conventionalcoatings, such as polymethacrylates and cellulose grades, for exampleHPMC, the pigment mixture according to the invention or the gold pigmentcan be employed in a variety of ways for colouring and finishing theproducts.

The invention thus also relates to formulations comprising the pigmentmixture according to the invention.

The invention likewise relates to formulations comprising the pigmentmixture according to the invention comprising components A and B incombination with water, polyols, polar and non-polar oils, fats, waxes,film formers, polymers, copolymers, surfactants, free-radicalscavengers, antioxidants, stabilisers, odour enhancers, silicone oils,emulsifiers, solvents, preservatives, thickeners, rheological additives,fragrances, UV absorbers, surface-active assistants and/or cosmeticactive compounds.

The following examples are intended to explain the invention, butwithout limiting it.

EXAMPLES Example 1

100 g of mica having a particle size of 10-60 μm are heated to 75° C. in2 l of demineralised water. When this temperature has been reached, amixed solution of 157.5 g of TiCl₄ (30% by weight of TiCl₄), 236.6 g ofFeCl₃ solution (11.7% of Fe), 5.9 g of AlCl₃×6 H₂O and 60 g ofdemineralised water is slowly metered in with vigorous stirring. The pHis kept constant at pH 2.6 using 32% sodium hydroxide solution. Whenthis solution has been added, the mixture is stirred for about a further15 minutes. The pH is subsequently raised to pH=7.5 using 32% sodiumhydroxide solution, and 431 g of sodium water-glass solution (13.5% ofSiO₂) are slowly metered in at this pH. The pH is then lowered to 2.0using 10% hydrochloric acid, the mixture is stirred for a further 15minutes, and 393 g of TiCl₄ solution (370 g of TiCl₄/l) are metered in.During this addition, the pH is kept constant using 32% sodium hydroxidesolution. The pH is subsequently raised to 2.9 using 32% sodiumhydroxide solution, and a solution consisting of 34 g of FeCl₃×6 H₂O and49 g of demineralised water is slowly metered in. The pH is keptconstant at pH=2.9 using 32% sodium hydroxide solution. When thissolution has been added, the mixture is stirred for about a further 15minutes. The pH is subsequently raised to pH=5.0 using 32% sodiumhydroxide solution, and the mixture is stirred for a further 15 minutes.

The pigment is filtered off, washed with demineralised water and driedat 110° C. for 16 h. Finally, the pigment is calcined at 850° C. for 30minutes, giving a gold pigment having an intense colour, high hidingpower and strong lustre.

The intensely lustrous gold pigment has the following L,a,b values:

(Phyma 22.5′122.5°, black background):L=771; a=1.4; b=32.2

Example 2

100 g of mica having a particle size of 10-60 μm are heated to 75° C. in2 l of demineralised water. When this temperature has been reached, amixed solution of 215 g of FeCl₃×6 H₂O (11.7% of Fe), 144 g of TiCl₄solution (30% by weight of TiCl₄) and 5.4 g of AlCl₃×6 H₂O and 50 g ofdemineralised water is slowly metered in with vigorous stirring. The pHis kept constant at pH 2.6 using 32% sodium hydroxide solution. Whenthis solution has been added, the mixture is stirred for about a further15 minutes. The pH is subsequently raised to pH=7.5 using 32% sodiumhydroxide solution, and 394 g of sodium water-glass solution (13.5% ofSiO₂) are slowly metered in at this pH. The pH is then lowered to 2.0using 10% hydrochloric acid. The mixture is stirred for a further 15minutes, and 314 g of TiCl₄ solution (370 g of TiCl₄/l) are then meteredin. During this addition, the pH is kept constant using 32% sodiumhydroxide solution. The pH is subsequently raised to 2.9 using 32%sodium hydroxide solution, and a solution consisting of 86 g of FeCl₃×6H₂O solution (11.7% of Fe) and 50 g of demineralised water is slowlymetered in. The pH is kept constant at 2.9 using 32% sodium hydroxidesolution. When this solution has been added, the mixture is stirred forabout a further 15 minutes. The pH is subsequently raised to pH=5.0using 32% sodium hydroxide solution, and the mixture is stirred for afurther 15 minutes.

The pigment is filtered off, washed with demineralised water and driedat 110° C. for 16 h. Finally, the pigment is calcined at 850° C. for 30minutes, giving a gold pigment having an intense colour, high hidingpower and strong lustre.

The intensely lustrous gold pigment has the following L,a,b values:

(Phyma 22.5°/22.5°, black background):L=80.0; a=−0.9; b=34.0

Example 3

100 g of mica having a particle size of 10-60 μm are heated to 75° C. in2 l of demineralised water. When this temperature has been reached, amixed solution of 215 g of FeCl₃×6 H₂O solution (11.7% of Fe), 144 g ofTiCl₄ solution (30% by weight of TiCl₄) and 5.4 g of AlCl₃×6 H₂O in 50 gof demineralised water is slowly metered in with vigorous stirring. ThepH is kept constant at pH 2.6 using 32% sodium hydroxide solution. Whenthis solution has been added, the mixture is stirred for about a further15 minutes. The pH is subsequently raised to pH=7.5 using 32% sodiumhydroxide solution, and 394 g of sodium water-glass solution (13.5% ofSiO₂) are slowly metered in at this pH. The pH is then lowered to 2.0using 10% hydrochloric acid, the mixture is stirred for a further 15minutes, and 235 g of TiCl₄ solution (370 g of TiCl₄/l) are metered in.During this addition, the pH is kept constant using 32% sodium hydroxidesolution. 22 g of sodium water-glass solution (13.5% of SiO₂) aresubsequently slowly metered in at pH=2.0, and the mixture is stirred fora further 15 minutes. The pH is then raised to 2.6 using 32% sodiumhydroxide solution, the mixture is stirred for a further 15 minutes, anda mixed solution consisting of 116 g of FeCl₃×6 H₂O (11.7% of Fe), 78 gof TiCl₄ solution (30% by weight of TiCl₄) and 2.5 g of AlCl₃×6 H₂O and30 g of demineralised water is slowly metered in. The pH is keptconstant at pH=2.6 using 32% sodium hydroxide solution. When thissolution has been added, the mixture is stirred for about a further 15minutes. The pH is subsequently raised to pH=5.0 using 32% sodiumhydroxide solution, and the mixture is stirred for a further 15 minutes.The pigment is filtered off, washed with demineralised water and driedat 110° C. for 16 h. Finally, the pigment is calcined at 850° C. for 30minutes, giving a gold pigment having an intense colour, high hidingpower and strong lustre.

The intensely lustrous gold pigment has the following L,a,b values:

(Phyma 22.5°/22.5°, black background):L=75.0; a=−1.2; b=28.3

Example 4

100 g of mica having a particle size of 10-60 μm are heated to 75° C. in2 l of demineralised water. When this temperature has been reached, amixed solution of 215 g of FeCl₃×6 H₂O solution (11.7% of Fe), 144 g ofTiCl₄ solution (30% by weight of TiCl₄) and 5.4 g of AlCl₃×6 H₂O and 50g of demineralised water is slowly metered in with vigorous stirring.The pH is kept constant at pH 2.6 using 32% sodium hydroxide solution.When this solution has been added, the mixture is stirred for about afurther 15 minutes. The pH is subsequently raised to pH=7.5 using 32%sodium hydroxide solution, and 394 g of sodium water-glass solution(13.5% of SiO₂) are slowly metered in at this pH. The pH is then loweredto 2.0 using 10% hydrochloric acid, the mixture is stirred for a further15 minutes, and a solution of 3.0 g of SnCl₄×5 H₂O and 10 ml ofhydrochloric acid (37% of HCl) in 100 ml of deionised water is added atthis pH. The pH is then lowered to 1.8 using 10% hydrochloric acid, themixture is stirred for a further 15 minutes, and 235 g of TiCl₄ solution(370 g of TiCl₄/l) are metered in. During this addition, the pH is keptconstant using 32% sodium hydroxide solution. The pH is then raised to2.6 using 32% sodium hydroxide solution, the mixture is stirred for afurther 15 minutes, and a mixed solution of 116 g of FeCl₃×6 H₂Osolution (11.7% of Fe), 78 g of TiCl₄ solution (30% by weight of TiCl₄)and 2.5 g of AlCl₃×6 H₂O and 30 g of demineralised water is slowlymetered in. The pH is kept constant at pH=2.6 using 32% sodium hydroxidesolution. After the metal-salt solution has been added, the mixture isstirred for about a further 15 minutes. The pH is subsequently raised topH=5.0 using 32% sodium hydroxide solution, and the mixture is stirredfor a further 15 minutes.

The pigment is filtered off, washed with demineralised water and driedat 110° C. for 16 h. Finally, the pigment is calcined at 850° C. for 30minutes, giving an intensely lustrous gold pigment having the followingL,a,b values:

(Phyma 22.5° 122.5°, black background): L=79.0;a=−0.9; b=31.7.

Use Examples Example 1A Shower Gel

Raw material INCI [%] A Ronastar ® Golden Sparks (1) CALCIUM ALUMINIUMBOROSILICATE, SILICA, 0.05 CI 77891 (TITANIUM DIOXIDE), TIN OXIDEMultilayer gold pigment (1) MICA, CI 77891 (TITANIUM DIOXIDE) Silica,0.10 according to Example 4 CI 77491 (IRON OXIDES), Alumina, Tin OxideKeltrol CG-SFT (2) XANTHAN GUM 1.10 Water, demineralised WATER, AQUA(WATER) 54.90 B Plantacare 2000 UP (3) DECYL GLUCOSIDE 20.00 Texapon ASV50 (3) SODIUM LAURETH SULFATE, SODIUM LAURETH-8, 3.60 SULFATE, MAGNESIUMLAURETH SULFATE, MAGNESIUM LAURETH-8 SULFATE, SODIUM OLETH, SULFATE,MAGNESIUM OLETH SULFATE Bronidox L (3) PROPYLENE GLYCOL 0.305-BROMO-5-NITRO-1,3-DIOXANE Frag 280851 Fruit Cocktail (4) PARFUM 0.200.1% of Sicovit Quinoline (5) AQUA (WATER), WATER, CI 47005 8.30 Yellow70 E 104 in water (ACID YELLOW 3), ACID YELLOW 3 0.1% of Dragocolor TrueBlue (6) AQUA (WATER), WATER, CI 42090 1.30 in water (FD&C BLUE NO. 1),FD&C BLUE NO. 1 C Citric acid monohydrate (1) CITRIC ACID 0.15 Water,demineralised WATER, AQUA (WATER) 10.00

Preparation:

Phase A: Introduce the water into the reactor and stir in the pigment.Scatter in the Keltrol CG-SFT slowly with stirring and stir until it hascompletely dissolved (do not homogenise). Add the constituents of phaseB individually to phase A. Dissolve the citric acid monohydrate in waterand add to the batch, and stir slowly until everything is homogeneouslydistributed. Adjust the pH to 6.0-6.5 with the addition of citric acid(if necessary).

Sources of Supply: (1) Merck KGaA/Rona® (2) C. P. Kelco (3) Cognis GmbH(4) Drom (5) BASF AG (6) Symrise Example 2A Eye Shadow

Raw material INCI [%] A Multilayer gold pigment (1) MICA, CI 77891(TITANIUM DIOXIDE) Silica, 25.00 according to Example 4 CI 77491 (IRONOXIDES), Alumina, Tin Oxide Timiron ® Splendid Gold (1) CI77891(TITANIUM DIOXIDE), MICA, SILICA 5.00 Talc (1) TALC 49.50 Potatostarch (2) POTATO STARCH, SOLANUM TUBEROSUM 7.50 (POTATO STARCH)Magnesium stearate (1) MAGNESIUM STEARATE 2.50 B Isopropyl stearate (3)ISOPROPYL STEARATE 9.34 Cetyl palmitate (1) CETYL PALMITATE 0.53 Ewalin1751 (4) PETROLATUM 0.53 Perfume oil Elegance + 79228 (5) PARFUM 0.20 DMF Propyl 4-hydroxybenzoate (1) PROPYLPARABEN 0.10

Preparation:

Combine and pre-mix the constituents of phase A. Subsequently add themolten phase B dropwise to the powder mixture with stirring. Introducethe powders into powder pans of large diameter and press at 80 bar.

Sources of Supply: (1) Merck KGaA/Rona® (2) Suedstaerke GmbH (3) CognisGmbH (4) H. Erhard Wagner GmbH (5) Symrise Example 3A Day Cream (O/W)

Raw material INCI [%] A Ronasphere ® LDP (1) SILICA, CI 77891 (TITANIUMDIOXIDE), CI 77491 5.00 (IRON OXIDES) Multilayer gold pigment (1) MICA,CI 77891 (TITANIUM DIOXIDE) Silica, 0.10 according to Example 4 CI 77491(IRON OXIDES), Alumina, Tin Oxide Veegum HV (2) MAGNESIUM ALUMINIUMSILICATE 1.00 Karion F liquid (1) SORBITOL 3.00 Methyl 4-hydroxybenzoate(1) METHYLPARABEN 0.18 Water, demineralised AQUA (WATER) 56.34 B Arlacel165 VP (3) GLYCERYL STEARATE, PEG-100 STEARATE 5.00 Lanette O (4)CETEARYL ALCOHOL 1.50 Miglyol 812 N (5) CAPRYLIC/CAPRIC TRIGLYCERIDE7.00 Shea butter solid (6) BUTYROSPERMUM PARKII (SHEA BUTTER) 2.00Cetiol SN (4) CETEARYL ISONONANOATE 7.00 Eutanol G (4) OCTYLDODECANOL7.50 Emulgade PL 68/50 (4) CETEARYL ALCOHOL, CETEARYL GLUCOSIDE 2.00Propyl 4-hydroxybenzoate (1) PROPYLPARABEN 0.08 C Perfume oil 200 530(7) PARFUM 0.20 Dow Corning 345 (8) CYCLOMETHICONE 2.00 Euxyl K 400 (9)PHENOXYETHANOL, METHYLDIBROMO, 0.10 GLUTARONITRILE Citric acidmonohydrate (1) CITRIC ACID 0.00

Preparation:

Warm phase B until the solution is clear. Disperse the Veegum in thewater of phase A, add the remaining raw materials, heat to 80° C. andadd phase B. Homogenise phase NB. Cool to 40° C. with stirring and addphase C. Cool to room temperature and adjust to pH 6.0.

Sources of Supply: (1) Merck KGaA/Rona® (2) Vanderbilt (3) Uniqema (4)Cognis GmbH (5) Sasol Germany GmbH (6) H. Erhard Wagner GmbH (7)Fragrance Resources (8) Dow Corning (9) Schülke & Mayr GmbH Example 4ASparkling Body Cream (O/W)

Raw material INCI [%] A Ronastar ® Golden Sparks (1) CALCIUM ALUMINIUMBOROSILICATE, SILICA, 1.00 CI 77891(TITANIUM DIOXIDE), TIN OXIDEMultilayer gold pigment (1) MICA, CI 77891(TITANIUM DIOXIDE), SILICA,1.00 according to Example 4 CI 77491(IRON OXIDES), ALUMINA, TIN OXIDEWater, demineralised WATER, AQUA (WATER) 40.60 Carbopol Ultrez 21 (2)ACRYLATES/C10-30 ALKYL ACRYLATE CROSS- 0.60 POLYMER Citric acidmonohydrate (1) CITRIC ACID 0.00 B Water, demineralised WATER, AQUA(WATER) 26.35 1,2-Propanediol (1) PROPYLENE GLYCOL 3.00 RonaCare ®allantoin (1) ALLANTOIN 0.20 C Paraffin liquid (1) PARAFFINUM LIQUIDUM(MINERAL OIL), 10.00 MINERAL OIL Cetiol V (3) DECYL OLEATE 6.00Hostaphat KL 340 D (4) TRILAURETH-4 PHOSPHATE 3.00 Cetyl alcohol (1)CETYL ALCOHOL 2.00 Phenonip (5) PHENOXYETHANOL, BUTYLPARABEN, ETHYL-0.50 PARABEN, PROPYLPARABEN, METHYLPARABEN D Water, demineralised WATER,AQUA (WATER) 3.50 Triethanolamine TRIETHANOLAMINE 0.35 E Germall 115 (6)IMIDAZOLIDINYL UREA 0.30 Perfume oil Vogue (7) PARFUM 0.10 Water,demineralised WATER, AQUA (WATER) 1.50

Preparation:

Disperse the pearlescent pigment in the water of phase A. If necessary,acidify using a few drops of citric acid in order to reduce theviscosity. Scatter in the Carbopol with stirring. When completelydissolved, slowly stir in the pre-dissolved phase B. Heat phase NB andphase C to 80° C., stir phase C into phase NB, homogenise with phase D,neutralise, homogenise again and cool with stirring. Dissolve theGermall 115 in the water of phase E at 40° C., add with stirring. Thenadd the perfume oil and cool to room temperature with stirring.

Sources of Supply: (1) Merck KGaA/Rona® (2) Noveon (3) Cognis GmbH (4)Clariant GmbH (5) Nipa Laboratorien GmbH (6) ISP Global Technologies (7)Drom Example 5A Creamy Eye Shadow

Raw material INCI [%] A Multilayer gold pigment (1) MICA, CI77891(TITANIUM DIOXIDE), SILICA, 20.00 according to Example 4 CI77491(IRON OXIDES), ALUMINA, TIN OXIDE Micronasphere ® M (1) MICA,SILICA 6.00 Unipure Green LC 789 CF (2) CI 77289 (CHROMIUM HYDROXIDEGREEN) 4.00 B Crodamol PMP (3) PPG-2 MYRISTYL ETHER PROPIONATE 37.80Syncrowax HGLC (3) C18-36 ACID TRIGLYCERIDE 10.00 Syncrowax HRC (3)TRIBEHENIN 3.00 Miglyol 812 N (4) CAPRYLIC/CAPRIC TRIGLYCERIDE 14.00Stearic acid (1) STEARIC ACID 3.00 Antaron V-216 (5) PVP/HEXADECENECOPOLYMER 2.00 Oxynex ® K liquid (1) PEG-8, TOCOPHEROL, ASCORBYLPALMITATE, 0.10 ASCORBIC ACID, CITRIC ACID Propyl 4-hydroxybenzoate (1)PROPYLPARABEN 0.10

Preparation:

Heat phase B to about 80° C. until everything has melted and cool to 65°C. Then add the pearlescent pigment, Micronasphere and the groundchromium oxide of phase A with stirring. Transfer the eye shadow intocontainers at 65° C.

Sources of Supply: (1) Merck KGaA/Rona® (2) Les Colorants Wackherr (3)Croda GmbH (4) Sasol Germany GmbH (5) ISP Global Technologies Example 6AHair Styling Gel

Raw material INCI [%] A Ronastar ® Golden Sparks (1) CALCIUM ALUMINIUMBOROSILICATE, CI 77891 2.55 (TITANIUM DIOXIDE), SILICA, TIN OXIDEMultilayer gold pigment (1) MICA, CI 77891 (TITANIUM DIOXIDE) Silica,0.10 according to Example 4 CI 77491 (IRON OXIDES), Alumina, Tin OxideCarbopol Ultrez 21 (2) ACRYLATES/C10-30 ALKYL ACRYLATE CROSS- 0.90POLYMER Water, demineralised WATER, AQUA (WATER) 50.35 B Luviskol K 30powder (3) PVP 2.00 Germaben II (4) PROPYLENE GLYCOL, DIAZOLIDINYL UREA,1.00 METHYLPARABEN, PROPYLPARABEN Triethanolamine, extra pure (1)TRIETHANOLAMINE 2.16 Water, demineralised WATER, AQUA (WATER) 40.94

Preparation:

Disperse the pearlescent pigments in the water of phase A and scatter inthe Carbopol with stirring. When completely dissolved, slowly stir inthe pre-dissolved phase B.

Sources of Supply: (1) Merck KGaA/Rona® (2) Noveon (3) BASF AG (4) ISPGlobal Technologies Example 7A Shampoo

Raw material INCI [%] A Multilayer gold pigment (1) MICA, CI77891(TITANIUM DIOXIDE), SILICA, 0.20 according to Example 4 CI77491(IRON OXIDES), ALUMINA, TIN OXIDE Carbopol ETD 2020 (2)ACRYLATES/C10-30 ALKYL ACRYLATE CROSS- 0.90 POLYMER Water, demineralisedAQUA (WATER) 63.40 B Triethanolamine, extra pure (1) TRIETHANOLAMINE0.90 Water, demineralised AQUA (WATER) 10.00 C Plantacare 2000 UP (3)DECYL GLUCOSIDE 20.00 Texapon ASV 50 (3) SODIUM LAURETH SULFATE, SODIUMLAURETH-8 4.35 SULFATE, MAGNESIUM LAURETH SULFATE, MAGNESIUM LAURETH-8SULFATE, SODIUM OLETH SULFATE, MAGNESIUM OLETH SULFATE Bronidox L (3)PROPYLENE GLYCOL, 5-BROMO-5-NITRO-1,3-DIOXANE 0.20 Perfume oil 200 524(4) PARFUM 0.05 Dye solution (q.s.) 0.00

Preparation:

For phase A, stir the pigment into the water. Acidify using a few dropsof citric acid (10%) in order to reduce the viscosity, and slowlyscatter in the Carbopol with stirring. When completely dissolved, slowlyadd phase B. Then add the constituents of phase C successively. Adjustthe pH to 6.0-6.5.

Sources of Supply: (1) Merck KGaA/Rona® (2) Noveon (3) Cognis GmbH (4)Fragrance Resources Example 8A Shimmering Body Powder

Raw material INCI [%] A Multilayer gold pigment (1) MICA, CI77891(TITANIUM DIOXIDE), SILICA, 10.00 according to Example 4 CI77491(IRON OXIDES), ALUMINA, TIN OXIDE B Microna ® Matte Red (1) CI77491 (IRON OXIDES), MICA 1.00 Microna ® Matte Yellow (1) MICA, CI 77492(IRON OXIDES) 1.00 Ronasphere ® LDP (1) SILICA, CI 77891 (TITANIUMDIOXIDE), CI 77491 4.00 (IRON OXIDES) Talc (1) TALC 25.00 Glass flakes(1) CALCIUM ALUMINIUM BOROSILICATE 15.00 White clay (1) KAOLIN 14.70Mica M (1) MICA 15.00 Silk mica (1) MICA 9.50 Propyl 4-hydroxybenzoate(1) PROPYLPARABEN 0.30 C Cetiol SQ (2) SQUALANE 2.00 Miglyol 812 N (3)CAPRYLIC/CAPRIC TRIGLYCERIDE 2.00 RonaCare ® tocopherol acetate (1)TOCOPHERYL ACETATE 0.20 Perfume (4) PARFUM 0.30

Preparation:

Weigh out all constituents of phase B together and grind homogeneouslyin a mixer. Subsequently add phase C and continue mixing, then add phaseA and grind briefly until the pearlescent pigment is uniformlydistributed.

Sources of Supply: (1) Merck KGaA/Rona® (2) Cognis GmbH (3) SasolGermany GmbH (4) Symrise Example 9A Long-Lasting Lip Gloss

Raw material INCI [%] A Multilayer gold pigment (1) MICA, CI77891(TITANIUM DIOXIDE), SILICA, 4.00 according to Example 4 CI 77491(IRON OXIDES), ALUMINA, TIN OXIDE Ronastar ® Golden Sparks (1) CALCIUMALUMINIUM BOROSILICATE, SILICA, 6.00 CI 77891 (TITANIUM DIOXIDE), TINOXIDE B Indopol H 100 (2) POLYBUTENE 30.00 Jojoba Glaze LV (3)SIMMONDSIA CHINENSIS (JOJOBA), JOJOBA, 20.00 SEED OIL,ETHYLENE/PROPYLENE/STYRENE COPOLYMER, BUTYLENE/ETHYLENE/STYRENECOPOLYMER Jojoba Glaze HV (3) SIMMONDSIA CHINENSIS (JOJOBA), JOJOBA,10.00 SEED OIL, ETHYLENE/PROPYLENE/STYRENE COPOLYMER,BUTYLENE/ETHYLENE/STYRENE COPOLYMER Castor oil (4) CASTOR OIL, RICINUSCOMMUNIS (CASTOR OIL) 23.15 Beeswax, bleached (1) BEESWAX, CERA ALBA(BEESWAX) 4.00 Propyl 4-hydroxybenzoate (1) PROPYLPARABEN 0.10 Oxynex ®K liquid (1) PEG-8, TOCOPHEROL, ASCORBYL PALMITATE, 0.05 ASCORBIC ACID,CITRIC ACID Jaune Covapate W 1761 (5) RICINUS COMMUNIS (CASTOR OIL), CI19140 1.00 (FD&C YELLOW No. 5 ALUMINIUM LAKE) C Neosil CT11 (6) SILICA1.50 Fragrance Tendresse 75418C (7) PARFUM 0.20

Preparation:

Weigh out all constituents of phase B together, heat to 80° C. and stirwell. Stir in the pigments of phase A, scatter in the Neosil withstirring, and finally add the perfume. Transfer the homogeneous mixtureinto containers.

Sources of Supply: (1) Merck KGaA/Rona® (2) BP Lavera Sud (3) DesertWhale (4) Henry Lamotte GmbH (5) Les Colorants Wackherr (6) IneosSilicas Limited (7) Symrise Example 10A Nail Varnish

Raw material INCI [%] Multilayer gold pigment (1) MICA, CI77891(TITANIUM DIOXIDE), SILICA. 1.75 according to Example 4 CI 77491(IRON OXIDES), ALUMINA, TIN OXIDE Ronastar ® Golden Sparks (1) CALCIUMALUMINIUM BOROSILICATE, SILICA, 0.25 CI 77891 (TITANIUM DIOXIDE), TINOXIDE Thixotropic nail varnish base (2) BUTYL ACETATE, ETHYL ACETATE,NITRO- 98.00 155 CELLULOSE, ACETYL TRIBUTYL CITRATE, PHTHALICANHYDRIDE/TRIMELLITIC ANHYDRIDE/GLYCOLS COPOLYMER, ISOPROPYL ALCOHOL,STEARALKONIUM HECTORITE, ADIPIC ACID/FUMARIC ACID/PHTHALICACID/TRICYCLODECANE DIMETHANOL COPOLYMER, CITRIC ACID

Preparation:

Weigh out the pigments together with the varnish base, mix well by handusing a spatula and subsequently stir at 1000 rpm for 10 min.

Sources of Supply: (1) Merck KGaA/Rona® (2) Durlin/Bergerac NC Example11A Volume Mascara (O/W)

Raw material INCI [%] A Mica Black (1) CI 77499 (IRON OXIDES), MICA, CI77891 5.00 (TITANIUM DIOXIDE) Colorona ® Red Brown (1) MICA, CI 77491(IRON OXIDES), CI 77891 3.00 (TITANIUM DIOXIDE) Multilayer gold pigment(1) MICA, CI 77891 (TITANIUM DIOXIDE) Silica, 2.00 according to Example4 CI 77491 (IRON OXIDES), Alumina, Tin Oxide Satin mica (1) MICA 2.00 BDermacryl 79 (2) ACRYLATES/OCTYLACRYLAMIDE COPOLYMER 3.50 Beeswax,bleached (1) BEESWAX, CERA ALBA (BEESWAX) 3.00 Syncrowax HRC (3)TRIBEHENIN 3.50 Stearic acid (1) STEARIC ACID 5.00 Tegin M (4) GLYCERYLSTEARATE 3.50 Tegosoft CT (4) CAPRYLIC/CAPRIC TRIGLYCERIDE 2.50 DowCorning 556 (5) PHENYL TRIMETHICONE 2.00 RonaCare ® tocopherol acetate(1) TOCOPHERYL ACETATE 0.50 Phenonip (6) PHENOXYETHANOL, BUTYLPARABEN,ETHYL- 0.80 PARABEN, PROPYLPARABEN, METHYLPARABEN C Water, demineralisedWATER, AQUA (WATER) 59.15 AMP Ultra PC 1000 (7) AMINOMETHYL PROPANOL1.25 1,3-Butanediol (1) BUTYLENE GLYCOL 1.00 RonaCare ® Biotin Plus (1)UREA, DISODIUM PHOSPHATE, BIOTIN, CITRIC 0.50 ACID D Germall 115 (8)IMIDAZOLIDINYL UREA 0.30 Water, demineralised WATER, AQUA (WATER) 1.50

Preparation:

Melt all constituents of phase B, apart from the Dermacryl 79, togetherat about 85° C., add the Dermacryl 79 with stirring, and stir for 20 minuntil everything is homogeneously distributed. Heat the constituents ofphase C to about 85° C. Stir the pearlescent pigments of phase A intophase C. Add phase C to phase B, continue stirring, and homogenise at8000 rpm using the Ultra-Turrax T25 for 1 min. Allow to cool withstirring, and add phase D at 40° C.

Sources of Supply: (1) Merck KGaA/Rona® (2) National Starch & Chemical(3) Croda GmbH (4) Degussa-Goldschmidt AG (5) Dow Corning (6) NipaLaboratorien GmbH (7) Angus Chemie GmbH (8) ISP Global TechnologiesExample 12A Tinted Day Cream with UV Protection (O/W)

Raw material INCI [%] A Eusolex ® 2292 (1) ETHYLHEXYL METHOXYCINNAMATE,BHT 3.00 Eusolex ® 4360 (1) BENZOPHENONE-3 3.00 Arlacel 165 VP (2)GLYCERYL STEARATE, PEG-100 STEARATE 5.00 Eusolex ® HMS (1) HOMOSALATE5.00 Arlacel 165 VP (2) GLYCERYL STEARATE, PEG-100 STEARATE 3.00Montanov 68 (3) CETEARYL ALCOHOL, CETEARYL GLUCOSIDE 3.00 Dow Corning345 (4) CYCLOMETHICONE 0.50 Eutanol G (5) OCTYLDODECANOL 2.00 Propyl4-hydroxybenzoate (1) PROPYLPARABEN 0.05 B Eusolex ® T-2000 (1) TITANIUMDIOXIDE, ALUMINA, SIMETHICONE 3.00 Extender W (1) MICA, CI 77891(TITANIUM DIOXIDE) 4.00 Microna ® Matte Yellow (1) MICA, CI 77492 (IRONOXIDES) 2.00 Microna ® Matte Orange (1) MICA, CI 77491 (IRON OXIDES)0.20 Microna ® Matte Red (1) CI 77491 (IRON OXIDES), MICA 0.20 Microna ®Matte Black (1) CI 77499 (IRON OXIDES), MICA 0.20 Multilayer goldpigment (1) MICA, CI 77891 (TITANIUM DIOXIDE) Silica, 2.00 according toExample 4 CI 77491 (IRON OXIDES), Alumina, Tin Oxide Karion FP, liquid(1) SORBITOL 5.00 RonaCare ® allantoin (1) ALLANTOIN 0.50 Keltrol T (6)XANTHAN GUM 0.20 Chemag 2000 (7) IMIDAZOLIDINYL UREA 0.30 Euxyl K 400(8) PHENOXYETHANOL, METHYLDIBROMO 0.10 GLUTARONITRILE Methyl4-hydroxybenzoate (1) METHYLPARABEN 0.15 Water, demineralised AQUA(WATER) 57.60

Preparation:

Disperse all constituents, apart from the Keltrol T, in the water ofphase B. Scatter the Keltrol into phase B with stirring, and, after 15minutes, heat to 80° C. Heat phase A to 75° C. Slowly stir phase B intophase A and homogenise. Cool with stirring.

Sources of Supply: (1) Merck KGaA/Rona® (2) Uniqema (3) Seppic (4) DowCorning (5) Cognis GmbH (6) C. P. Kelco (7) Chemag AG (8) Schülke & MayrGmbH Example 13A Cream Conditioner

Phase Raw material INCI % A Water Aqua (water) 79.7 Multilayer gold (1)MICA, CI 77891 (TITANIUM 0.50 pigment according DIOXIDE) Silica, CI77491 to Example 4 (IRON OXIDES), Alumina, Tin Oxide Luviquat Hold (2)Polyquaternium-46 5.00 Luviquat PQ 11 (2) Polyquaternium-11 2.001,3-Butanediol (1) Butylene Glycol 3.00 B Cremophor A 6 (2) Ceteareth-6and Stearyl 3.00 Alcohol Ammonyx 4 (2) Stearalkonium chloride 3.00Lanette Wax O (3) Cetearyl Alcohol 2.00 Eusolex 2292 (1) OctylMethoxycinnamate 0.10 C RonaCare ® (1) Tocopheryl acetate 0.50tocopherol acetate RonaCare ® (1) Bisabolol 0.10 bisabolol nat. PerfumeParfum 0.10 Germaben II (4) Propylene glycol, 1.00 Diazolidinyl urea,Methylparaben, Propylparaben

Preparation:

Disperse the pigments in the water of phase A, and add the remaining rawmaterials. Stir after each addition and subsequently heat to 75° C. Mixthe raw materials of phase B, heat to 75-80° C. and add to phase A. Mixuntil a homogeneous distribution is present. Add phase C at 45° C.

Sources of Supply: (1) Merck KGaA/Rona® (2) BASF AG (3) Cognis GmbH (4)ISP Global Technologies

The cosmetic formulations of Examples 1A-13A are distinguished by theirintense golden lustre and their very good skin feel.

Example 14A Production of Hard Caramels

Raw material % Sources of supply: Sugar 41% Südzucker Water 17.118%   Glucose syrup 41% C* Sweet Cerestar, Krefeld Multilayer gold 0.082%(0.1% based on Merck KGaA, pigment according the pouring material)Darmstadt to Example 1 E 104 1:100 dil. 0.4% of Sikovit BASF,Ludwigshafen Aroma 0.4% (banana Dragaco, Holzminden 9/030388)

The sugar is heated to 100° C. with the water, and the glucose syrup isthen added. The solution is subsequently heated to 145° C. Afteraddition of the gold pigment, the colouring solution and the aroma, thecaramel solution is poured into greased moulds using a pouring funnel.Finally, the caramels are allowed to cool for two hours. The goldpigment can be added either mixed with the sugar or mixed with theglucose syrup. This variant contains no acid since this would make thecaramelisation too strong.

Example 15A Coating of Tablets

a) Initial weight 1 kg of white tablets d=8 mm, G=200 mg

Solution for film coating: 6% of Sepifilm Lp10 Seppic (mixture ofhydroxypropylmethyl- cellulose, stearic acid and micro- crystallinecellulose) 5% of multilayer gold pigment Merck KGaA, Darmstadt accordingto Example 2 89%  of water

Total application amount: 200 g

This corresponds to 1.2 mg of polymer/cm² of tablet surface

Preparation of the Film-Coating Solution:

-   -   Stir the gold pigment into the water. Subsequently add        additional dyes. Finally, scatter the film former (HPMC) into        the suspension. Due to the increasing viscosity, the stirring        speed must also be increased correspondingly. After about 40-60        minutes, the HPMC has completely dissolved and the solution can        then be sprayed onto the tablets.    -   The spray application is carried out by means of standard        coating methods.

1. A formulation comprising i) a pigment mixture comprising at least twocomponents A and B, characterised in that component A comprises effectpigments based on multicoated flake-form substrates which have a layersequence comprising (A) a high-refractive-index coating consisting of amixture of TiO₂ and Fe₂O₃ in the molar ratio 1:0.5 to 1:2.0 andoptionally one or more metal oxide(s) in amounts of <20% by weight,based on layer (A), (B) a colourless coating having a refractive indexn<1.8, (C) a colourless coating having a refractive index n>1.8, (D) anabsorbent coating having a refractive index n>1.8 and optionally (E) anouter protective layer, and component B comprises colorants selectedfrom the group of inorganic pigments, organic pigments, dyes, colouringnatural fruit and/or plant extracts and/or fillers which consist offlake-form, needle-shaped, spherical or irregularly shaped particles andii) one or more cosmetic active compounds.
 2. A formulation according toclaim 1, characterised in that the effect pigment of component A has thefollowing layer structure:substrate+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃/TiO₂substrate+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃substrate+Fe₂O₃/TiO₂+SiO₂+TiO₂+SiO₂+Fe₂O₃/TiO₂.
 3. A formulationaccording to claim 1, characterised in that the flake-form substrate ofcomponent A is covered with a layer of TiO₂ or SiO₂.
 4. A formulationaccording to claim 1, characterised in that the effect pigment ofcomponent A has the following layer structure:substrate+TiO₂+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃/TiO₂substrate+TiO₂+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃.
 5. A formulation according toclaim 1, characterised in that the molar ratio of TiO₂ and Fe₂O₃ oflayer (A) of the effect pigment of component A is 1:1.
 6. A formulationaccording to claim 1, characterised in that the molar ratio of TiO₂ andFe₂O₃ of layer (D) of the effect pigment of component A is 1:1.
 7. Aformulation according to claim 1, characterised in that layer (A) of theeffect pigment of component A is a layer of pseudobrookite or a mixtureof pseudobrookite with TiO₂ or pseudobrookite with Fe₂O₃.
 8. Aformulation according to claim 1, characterised in that layer (D) of theeffect pigment of component A is a layer of pseudobrookite or a mixtureof pseudobrookite with TiO₂ or pseudobrookite with Fe₂O₃.
 9. Aformulation according to claim 1, characterised in that layers (A) and(D) of the effect pigment of component A are each a layer ofpseudobrookite or a mixture of pseudobrookite with TiO₂ orpseudobrookite with Fe₂O₃.
 10. A formulation according to claim 1,characterised in that the colorant of component B is a pearlescentpigment, a multilayer pigment and/or an interference pigment or amixture thereof which is different from component A.
 11. A formulationaccording to claim 1, characterised in that component A and component Bare mixed in the mixing ratio 99:1 to 50:50.
 12. A formulation accordingto claim 1, characterised in that component A and component B are mixedin the mixing ratio 99:1 to 1:99, where component B is a filler.
 13. Aformulation according to claim 1, wherein the effect pigments ofcomponent A are based on multicoated flake-form substrates,characterised in that they have a layer sequence (IL), (A)-(D) or (IL)(A)-(E): (IL) a high-refractive-index coating of TiO₂, (A) ahigh-refractive-index coating consisting of a mixture of TiO₂ and Fe₂O₃in the molar ratio 1:0.5 to 1:2.0 and optionally one or more metaloxide(s) in amounts of <20% by weight, based on layer (A), (B) acolourless coating having a refractive index n<1.8, (C) a colourlesscoating having a refractive index n>1.8, (D) an absorbent coating havinga refractive index n>1.8 and optionally (E) an outer protective layer.14. A formulation according to claim 13, characterised in that theeffect pigments have the following layer structure:substrate+TiO₂+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃/TiO₂substrate+TiO₂+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃.
 15. A formulation accordingto claim 13, characterised in that the Fe₂O₃ and TiO₂ mixture within thehigh-refractive-index coating is pseudobrookite or a mixture of pseudobrookite with TiO₂ or pseudobrookite with Fe₂O₃.
 16. A method comprisingincluding a formulation of claim 13 in cosmetic formulations and in foodand pharmaceutical products.
 17. A method comprising including aformulation of claim 1 in cosmetic formulations and in food andpharmaceutical products.
 18. A method comprising including a formulationaccording to claim 1 in a food or pharmaceutical product, characterisedin that it is employed in combination with aroma substances and/orsweeteners.
 19. (canceled)
 20. A formulation of claim 1 comprising thepigment mixture according to claim 1 in amounts of 0.001-99% by weight,based on the formulation as a whole.
 21. A formulation according toclaim 20 characterised in that it additionally comprises water, polyols,polar and non-polar oils, fats, waxes, film formers, polymers,copolymers, surfactants, free-radical scavengers, antioxidants,stabilisers, odour enhancers, silicone oils, emulsifiers, solvents,preservatives, thickeners, rheological additives, fragrances, UVabsorbers and/or surface-active assistants.
 22. A formulation of claim 1wherein the colorant of component B is a pearlescent pigment, amultilayer pigment and/or an interference pigment or a mixture thereofwhich is different from component A.
 23. A formulation of claim 1wherein the one or more cosmetic active compounds is independentlyselected from the group consisting of insect repellents, inorganic UVfilters, organic UV filters, UV A/BC protective filters, anti-ageingactive compounds, vitamins and derivatives thereof, self-tanning agents,bisabolol, LPO, VTA, ectoine, emblica, allantoin, bioflavonoids andderivatives thereof.
 24. A formulation of claim 1 wherein the one ormore cosmetic active compounds includes one or more organic UV filtersin an amount of 0.5 to 10% by weight, preferably 1-8% by weight and/orone or more inorganic UV filters in an amount of 0.1 to 30% by weight,based on the formulation as a whole.
 25. A formulation of claim 1wherein the one or more cosmetic active compounds includes one or moreconventional skin-protecting or skin-care active compounds.
 26. Aformulation of claim 1 wherein the one or more cosmetic active compoundsincludes pyrimidinecarboxylic acids and/or aryl oximes.
 27. Aformulation of claim 1 wherein the one or more cosmetic active compoundsincludes ectoine and ectoine derivatives for the care of aged, dry orirritated skin.
 28. A formulation of claim 27 wherein the ectoinederivatives for the care of aged, dry or irritated skin comprisehydroxy-ectoine.
 29. A formulation of claim 27 wherein the ectoine andectoine derivatives for the care of aged, dry or irritated skin are usedin an amount of 0.05-5% by weight, based on the formulation.
 30. Aformulation of claim 27 wherein the ectoine and ectoine derivatives forthe care of aged, dry or irritated skin are used in an amount of 0.1-3%by weight, based on the formulation.
 31. A formulation of claim 1 whichis a powder, soap, surfactant-containing cleansing product, lipstick,rouge, care cream or sunscreen preparation.
 32. A method of preparing acosmetic composition or a food or a pharmaceutical composition,comprising incorporating a formulation into a cosmetic composition or afood or a pharmaceutical composition, wherein the formulation comprises:i) components A and B in a mixing ratio of 99:1 to 1:99, whereincomponent A comprises effect pigments based on multicoated flake-formsubstrates which have a layer sequence comprising (A) ahigh-refractive-index coating consisting of a mixture of TiO₂ and Fe₂O₃in the molar ratio 1:0.5 to 1:2.0 and optionally one or more metaloxide(s) in amounts of <20% by weight, based on layer (A), (B) acolourless coating having a refractive index n<1.8, (C) a colourlesscoating having a refractive index n>1.8, (D) an absorbent coating havinga refractive index n>1.8 and optionally (E) an outer protective layer,and component B comprises fillers which consist of flake-form,needle-shaped, spherical or irregularly shaped particles and ii) one ormore cosmetic active compounds.
 33. The method of claim 32 wherein theeffect pigments of component A have the following layer structure:substrate+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃/TiO₂substrate+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃substrate+Fe₂O₃/TiO₂+SiO₂+TiO₂+SiO₂+Fe₂O₃/TiO₂.
 34. The method of claim32 wherein the flake-form substrate is covered with a layer of TiO₂ orSiO₂.
 35. The method of claim 32 wherein the effect pigments ofcomponent A consist of:substrate+TiO₂+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃/TiO₂substrate+TiO₂+Fe₂O₃/TiO₂+SiO₂+TiO₂+Fe₂O₃.
 36. The method of claim 32wherein the molar ratio of TiO₂ and Fe₂O₃ of layer (A) of the effectpigment of component A is 1:1.
 37. The method of claim 32 wherein themolar ratio of TiO₂ and Fe₂O₃ of layer (D) of the effect pigment ofcomponent A is 1:1.
 38. The method of claim 32 wherein layer (A) of theeffect pigment of component A is a layer of pseudobrookite or a mixtureof pseudobrookite with TiO₂ or pseudobrookite with Fe₂O₃.
 39. The methodof claim 32 wherein layer (D) of the effect pigment of component A is alayer of pseudobrookite or a mixture of pseudobrookite with TiO₂ orpseudobrookite with Fe₂O₃.
 40. The method of claim 32 wherein layers (A)and (D) of the effect pigment of component A are each a layer ofpseudobrookite or a mixture of pseudobrookite with TiO₂ orpseudobrookite with Fe₂O₃.
 41. The method of claim 32 wherein componentA and component B are mixed in the mixing ratio 99:1 to 50:50.
 42. Themethod of claim 32 wherein the combination of components A and Bcomprise 0.01-99% by weight, of the formulation as a whole.
 43. Themethod of claim 32 wherein the formulation further comprises aromasubstances and/or sweeteners.